CN113785008B - Polyfunctional active ester compound, resin composition, cured product, and laminated film - Google Patents
Polyfunctional active ester compound, resin composition, cured product, and laminated film Download PDFInfo
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- CN113785008B CN113785008B CN202080033314.5A CN202080033314A CN113785008B CN 113785008 B CN113785008 B CN 113785008B CN 202080033314 A CN202080033314 A CN 202080033314A CN 113785008 B CN113785008 B CN 113785008B
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- C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D209/02—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom condensed with one carbocyclic ring
- C07D209/44—Iso-indoles; Hydrogenated iso-indoles
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- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
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Abstract
The purpose of the present invention is to provide a polyfunctional active ester compound which enables to obtain a resin composition having excellent heat resistance and dielectric characteristics after curing. The present invention also provides a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a laminate film using the resin composition. The present invention is a polyfunctional active ester compound represented by the following formula (1). In the formula (1), R 1 R is R 2 Each of which may be the same or different and is an optionally substituted aryl group, X is an oxygen atom or a 2-valent group, Y is a 2-valent organic group, and n is an integer of 1 or more.
Description
Technical Field
The present invention relates to a polyfunctional active ester compound capable of giving a resin composition excellent in heat resistance and dielectric characteristics after curing. The present invention also relates to a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a laminate film using the resin composition.
Background
Curable resins such as epoxy resins, which have low shrinkage and excellent adhesion, insulation and chemical resistance, are used in many industrial products. In particular, a resin composition used for an interlayer insulating material of a printed wiring board needs to have dielectric characteristics such as a low dielectric constant and a low dielectric loss tangent. As resin compositions excellent in such dielectric characteristics, for example, patent documents 1 and 2 disclose resin compositions containing a curable resin and a compound having a specific structure as a curing agent. However, such a resin composition has a problem that it is difficult to achieve both heat resistance and dielectric characteristics after curing.
Prior art literature
Patent literature
Patent document 1: japanese patent laid-open No. 2017-186551
Patent document 2: international publication No. 2016/114286
Disclosure of Invention
Problems to be solved by the invention
The purpose of the present invention is to provide a polyfunctional active ester compound which can give a resin composition excellent in heat resistance and dielectric characteristics after curing. The present invention also provides a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a laminate film using the resin composition.
Means for solving the problems
The present invention is a polyfunctional active ester compound represented by the following formula (1).
[ chemical formula 1]
In the formula (1), R 1 R is R 2 Each of which may be the same or different and is an optionally substituted aryl group, X is an oxygen atom or a 2-valent group, Y is a 2-valent organic group, and n is an integer of 1 or more.
The present invention will be described in detail below.
The present inventors have found that a resin composition excellent in heat resistance and dielectric characteristics after curing can be obtained by using a polyfunctional active ester compound having a specific structure as a curing agent, and completed the present invention.
The polyfunctional active ester compound of the present invention is represented by the above formula (1).
In the above formula (1), R 1 R is R 2 Each of which may be the same or different and is an optionally substituted aryl group. By having optionally substituted aryl as R above 1 R is as described above 2 Thus, the cured product of the obtained resin composition is excellent in dielectric characteristics such as low dielectric loss tangent.
Examples of the aryl group include: phenyl, naphthyl, anthracenyl, and the like.
Examples of the substituent when the aryl group is substituted include: aliphatic groups, and the like.
Wherein R in the above formula (1) 1 R is R 2 The group represented by the following formula (2) is preferable. By making R as described above 1 R is as described above 2 In the case where the polyfunctional active ester compound of the present invention is used as a curing agent, the resulting cured product of the resin composition is further excellent in dielectric characteristics such as low dielectric loss tangent.
[ chemical formula 2]
In the formula (2), R 3 Each independently is a hydrogen atom or an aliphatic group, and each is a bonding position.
In the above formula (1), X is an oxygen atom or a 2-valent group, and X may be different from each other. Among them, the above X is preferably an oxygen atom, a sulfonyl group, a carbonyl group or a group represented by the following formula (3), more preferably an oxygen atom or a group represented by the following formula (3).
[ chemical formula 3]
In formula (3), the bond position is.
In the above formula (1), Y is a 2-valent organic group. Wherein, the above Y is preferably an optionally substituted arylene group. By making Y an optionally substituted arylene group, the heat resistance of the cured product of the obtained resin composition becomes excellent.
Examples of the arylene group in the case where Y in the above formula (1) is an optionally substituted arylene group include: phenylene, naphthylene, anthracenylene, and the like.
Examples of the substituent when the arylene group is substituted include an aliphatic group and the like.
Among them, Y in the above formula (1) is preferably 1, 3-phenylene or 1, 4-phenylene.
In the above formula (1), n is an integer of 1 or more. The number average molecular weight of the polyfunctional active ester compound represented by the formula (1) may be in the range described below, and is preferably 1 or more and 5 or less, more preferably 1 or 2.
The polyfunctional active ester compound of the present invention has a number average molecular weight of preferably 1300 at a lower limit and 5500 at an upper limit. By setting the number average molecular weight in this range, the compatibility between the polyfunctional active ester compound of the present invention and the resin component becomes more excellent, and the dielectric characteristics such as low dielectric loss tangent of the cured product of the obtained resin composition becomes more excellent. The polyfunctional active ester compound of the present invention has a more preferable lower limit of 1400 in number average molecular weight, a more preferable upper limit of 2700 and a particularly preferable lower limit of 1800.
In the present specification, the "number average molecular weight" is a value obtained by measuring by Gel Permeation Chromatography (GPC) using tetrahydrofuran as a solvent and converting the obtained product into polystyrene. Examples of the column used for measuring the number average molecular weight in terms of polystyrene by GPC include JAIGEL-2H-A (manufactured by Japanese analytical industries Co., ltd.).
The polyfunctional active ester compound of the present invention is preferably a compound represented by the following formula (4) in view of particularly excellent heat resistance and dielectric characteristics of a cured product of the obtained resin composition.
[ chemical formula 4]
Examples of the method for producing the polyfunctional active ester compound of the present invention include the following methods.
Namely, there can be mentioned: and a method in which an acid dianhydride represented by the following formula (5) and an aminophenol represented by the following formula (6) are reacted with a dicarboxylic acid represented by the following formula (7) and an aromatic monocarboxylic acid represented by the following formula (8-1) and/or an aromatic monocarboxylic acid represented by the following formula (8-2).
Specifically, an aminophenol represented by the following formula (6) is dissolved in a solvent capable of dissolving an amic acid compound obtained by the reaction, and an acid dianhydride represented by the following formula (5) is added to the obtained solution to react to obtain a solution of the amic acid compound. Examples of the solvent include: n-methylpyrrolidone, dimethylformamide, dimethylacetamide and the like. Then, the solvent is removed from the obtained solution of the amic acid compound by heating, reducing pressure or the like, or the amic acid oligomer is recovered by reprecipitation by pouring into a poor solvent such as water, methanol, hexane or the like, and further the imidization reaction is carried out by heating at about 200 ℃ or more for 1 hour or more, whereby an imide compound having phenolic hydroxyl groups at both ends is obtained. Then, the obtained imide compound is subjected to an esterification reaction with a dicarboxylic acid represented by the following formula (7) or a halide thereof. Further, the multifunctional active ester compound of the present invention can be obtained by an esterification reaction with an aromatic monocarboxylic acid represented by the following formula (8-1) or a halide thereof and/or an aromatic monocarboxylic acid represented by the following formula (8-2) or a halide thereof.
The number average molecular weight of the polyfunctional active ester compound of the present invention can be adjusted by, for example, the following method.
That is, in the step of reacting the dicarboxylic acid represented by the following formula (7) or a halide thereof with the imide compound having a phenolic hydroxyl group at both ends, the number average molecular weight can be adjusted by adjusting the equivalent ratio of the dicarboxylic acid represented by the following formula (7) or a halide thereof to the imide compound having a phenolic hydroxyl group at both ends, and the reaction time. Alternatively, purification by GPC may be performed before or after the reaction of the aromatic monocarboxylic acid represented by the following formula (8-1) or a halide thereof and/or the esterification reaction of the aromatic monocarboxylic acid represented by the following formula (8-2) or a halide thereof. N in the above formula (1) can be similarly adjusted.
[ chemical formula 5]
In the formula (5), X is the same group as X in the above formula (1).
[ chemical formula 6]
[ chemical formula 7]
In the formula (7), Y is the same group as Y in the above formula (1).
[ chemical formula 8]
In the formula (8-1), R 1 Is R in the formula (1) 1 The same groups, in the formula (8-2), R 2 Is R in the formula (1) 2 The same groups.
Examples of the acid dianhydride represented by the above formula (5) include: 3,3 '-oxydiphthalic dianhydride, 3,4' -oxydiphthalic dianhydride, 4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, anhydride of 4,4 '-bis (3, 4-dicarboxyphenoxy) diphenyl ether, p-phenylene bis (trimellitic anhydride), 4' -carbonyldiphthalic dianhydride, and the like. Among them, 4' -oxydiphthalic anhydride and 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride are preferable, and 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride is more preferable, from the viewpoints of excellent solubility, heat resistance and availability.
Examples of the aminophenol represented by the above formula (6) include: 3-aminophenol, 4-aminophenol, and the like.
Examples of the dicarboxylic acid represented by the above formula (7) include: terephthalic acid, isophthalic acid, 4' -oxybisbenzoic acid, 2, 7-naphthalene dicarboxylic acid, and the like. Among them, terephthalic acid and isophthalic acid are preferable.
Examples of the aromatic monocarboxylic acid represented by the above formula (8-1) and the aromatic monocarboxylic acid represented by the above formula (8-2) include: 1-naphthoic acid, 2-naphthoic acid, 1-anthranilic acid, 2-anthranilic acid, 9-anthranilic acid, phenanthrene carboxylic acid, pyrenecarboxylic acid, and the like. Among them, 2-naphthoic acid is preferable.
In addition, a resin composition containing a curable resin and the polyfunctional active ester compound of the present invention is also one of the present invention. The resin composition of the present invention contains the polyfunctional active ester compound of the present invention, and thus the cured product is excellent in heat resistance and dielectric characteristics. Accordingly, the resin composition of the present invention is suitable for forming an insulating layer in a multilayer printed wiring board.
In order to improve processability in an uncured state, the resin composition of the present invention may contain a curing agent in addition to the polyfunctional active ester compound of the present invention within a range that does not hinder the object of the present invention.
Examples of the other curing agent include: phenolic curing agents, thiol curing agents, amine curing agents, acid anhydride curing agents, cyanate curing agents, and other active ester curing agents other than the polyfunctional active ester compounds of the present invention. Among them, the active ester-based curing agent other than the polyfunctional active ester compound of the present invention is preferably a cyanate-based curing agent.
When only the polyfunctional active ester compound of the present invention is used as the above-mentioned curing agent, the content of the polyfunctional active ester compound of the present invention is preferably 0.3 equivalent at a lower limit and 2.0 equivalent at an upper limit relative to 1 equivalent of the curable resin. When only the polyfunctional active ester compound of the present invention is used as the curing agent, the content of the polyfunctional active ester compound of the present invention is in this range, whereby the heat resistance and dielectric characteristics of the obtained resin composition are further excellent. When only the polyfunctional active ester compound of the present invention is used as the above-mentioned curing agent, the more preferable lower limit of the content of the polyfunctional active ester compound of the present invention is 0.6 equivalent, and the more preferable upper limit is 1.5 equivalent.
In addition, when the polyfunctional active ester compound of the present invention is used in combination with other curing agents as the curing agent, the content of the polyfunctional active ester compound of the present invention is preferably 0.05 equivalent at a lower limit of 1 equivalent to the curable resin, and is preferably 1.8 equivalent at an upper limit. When the polyfunctional active ester compound of the present invention is used in combination with other curing agents as the curing agent, the content of the polyfunctional active ester compound of the present invention is in this range, whereby the heat resistance and dielectric characteristics of the obtained resin composition become more excellent. When the polyfunctional active ester compound of the present invention is used in combination with other curing agents as the above-mentioned curing agents, the more preferable lower limit of the content of the polyfunctional active ester compound of the present invention is 0.2 equivalent, and the more preferable upper limit is 1.2 equivalent. When the polyfunctional active ester compound of the present invention and the other curing agent are used in combination as the curing agent, the total content of the polyfunctional active ester compound of the present invention and the other curing agent is preferably 0.3 equivalent at a lower limit and 2.0 equivalent at an upper limit, relative to 1 equivalent of the curable resin.
The resin composition of the present invention contains a curable resin.
Examples of the curable resin include: epoxy resins, cyanate resins, phenol resins, imide resins, maleimide resins, benzoxazine resins, silicone resins, acrylic resins, fluorine resins, and the like. Among them, the curable resin preferably contains at least 1 selected from the group consisting of epoxy resins, cyanate resins, phenol resins, imide resins, maleimide resins, and benzoxazine resins, and more preferably contains an epoxy resin. The curable resin may be used alone or in combination of 2 or more.
Examples of the epoxy resin include: bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol E type epoxy resin, bisphenol S type epoxy resin, 2' -diallyl bisphenol A type epoxy resin, hydrogenated bisphenol type epoxy resin, propylene oxide addition bisphenol A type epoxy resin, resorcinol type epoxy resin, biphenyl type epoxy resin, thioether type epoxy resin, diphenyl ether type epoxy resin, dicyclopentadiene type epoxy resin, naphthalene type epoxy resin, fluorene type epoxy resin, naphthylene ether type epoxy resin, phenol novolac type epoxy resin, o-cresol novolac type epoxy resin, dicyclopentadiene novolac type epoxy resin, biphenyl novolac type epoxy resin, naphthol novolac type epoxy resin, glycidol amine type epoxy resin, alkyl polyol type epoxy resin, rubber modified type epoxy resin, glycidyl ester compound, and the like.
The resin composition of the present invention preferably contains a curing accelerator. By containing the above curing accelerator, the curing time can be shortened and productivity can be improved.
Examples of the curing accelerator include: imidazole-based curing accelerators, tertiary amine-based curing accelerators, phosphine-based curing accelerators, photobase generators, sulfonium salt-based curing accelerators, and the like. Among them, imidazole-based curing accelerators and phosphine-based curing accelerators are preferable from the viewpoints of storage stability and curability.
The curing accelerators may be used alone or in combination of 2 or more.
The lower limit of the content of the curing accelerator is preferably 0.01 parts by weight, and the upper limit is preferably 10 parts by weight, based on 100 parts by weight of the curable resin. When the content of the curing accelerator is within this range, the effect of shortening the curing time is more excellent without deteriorating the adhesiveness of the obtained resin composition. The lower limit of the content of the above-mentioned curing accelerator is more preferably 0.03 parts by weight, the upper limit is more preferably 4 parts by weight, the lower limit is more preferably 0.05 parts by weight, and the upper limit is more preferably 3 parts by weight.
The resin composition of the present invention preferably further contains an inorganic filler.
By containing the inorganic filler, the adhesive property, processability, electrical characteristics, and heat resistance of the cured product of the resin composition of the present invention are further improved.
The inorganic filler is preferably at least one of silica and alumina. By containing at least one of silica and alumina as the inorganic filler, the resin composition of the present invention is more excellent in adhesion, processability, electrical characteristics, and heat resistance of a cured product. The inorganic filler is more preferably silica, and still more preferably fused silica.
Examples of the inorganic filler other than the silica and the alumina include: barium sulfate, talc, clay, mica, magnesium oxide, aluminum hydroxide, aluminum nitride, boron nitride, silicon nitride, glass frit, glass fiber, carbon fiber, inorganic ion exchanger, and the like.
The inorganic filler may be used alone or in combination of 2 or more.
The average particle diameter of the inorganic filler is preferably 50nm in lower limit and 5 μm in upper limit. When the average particle diameter of the inorganic filler is within this range, the resulting resin composition is further excellent in coatability and processability. The average particle diameter of the inorganic filler is more preferably 75nm in lower limit, more preferably 3 μm in upper limit, still more preferably 100nm in lower limit, and still more preferably 2 μm in upper limit.
The average particle size of the inorganic filler and the flow control agent described later can be measured by dispersing the inorganic filler and the flow control agent in a solvent (water, organic solvent, etc.), for example, using a particle size distribution measuring apparatus. Examples of the particle size distribution measuring apparatus include NICOMP 380ZLS (manufactured by PARTICLE SIZING SYSTEMS).
The content of the inorganic filler in 100 parts by weight of the solid content of the resin composition of the present invention is preferably 50 parts by weight, and the upper limit is preferably 85 parts by weight. When the content of the inorganic filler is within this range, the resulting resin composition is more excellent in adhesion, processability, electrical characteristics, and heat resistance of the cured product. The lower limit of the content of the inorganic filler is more preferably 55 parts by weight, and the upper limit is more preferably 80 parts by weight.
The term "solid component" as used herein means the total of the components of the resin composition excluding the solvent, when the solvent described later is used.
The resin composition of the present invention may contain a flow regulator for the purpose of improving the coatability and shape retention properties of an adherend in a short period of time.
Examples of the flow regulator include fumed silica such as AEROSIL and a layered silicate.
The above-mentioned flow regulators may be used alone or in combination of 2 or more.
Further, as the flow regulator, a flow regulator having an average particle diameter of less than 50nm is suitably used.
The content of the flow regulator is preferably 0.1 part by weight at a lower limit, and preferably 100 parts by weight at an upper limit, based on 100 parts by weight of the curable resin. By setting the content of the flow regulator to this range, the effect of improving the coating property and shape retention property of the adherend in a short time becomes more excellent. The content of the above-mentioned flow regulator is more preferably limited to 0.5 parts by weight, and the more preferably limited to 50 parts by weight.
The resin composition of the present invention may contain an organic filler for the purpose of stress relaxation, toughness, and the like.
Examples of the organic filler include: silicone rubber particles, acrylic rubber particles, urethane rubber particles, polyamide particles, polyamideimide particles, polyimide particles, benzoguanamine particles, core-shell particles thereof, and the like. Among them, polyamide particles, polyamideimide particles, and polyimide particles are preferable.
The organic filler may be used alone or in combination of 2 or more.
The preferable upper limit of the content of the organic filler in 100 parts by weight of the solid content of the resin composition of the present invention is 300 parts by weight. When the content of the organic filler is within this range, the toughness and the like of the cured product of the obtained resin composition become more excellent while maintaining excellent adhesion and the like. The more preferable upper limit of the content of the organic filler is 200 parts by weight.
The resin composition of the present invention may contain a flame retardant.
Examples of the flame retardant include: boehmite type aluminum hydroxide, magnesium hydroxide, halogen-based compounds, phosphorus-based compounds, nitrogen compounds, and the like. Among them, boehmite type aluminum hydroxide is preferable.
The above flame retardants may be used alone or in combination of 2 or more.
The lower limit of the content of the flame retardant is preferably 2 parts by weight, and the upper limit is preferably 300 parts by weight, based on 100 parts by weight of the curable resin. When the content of the flame retardant is within this range, the flame retardancy is excellent while the obtained resin composition maintains excellent adhesion and the like. The lower limit of the content of the above flame retardant is more preferably 5 parts by weight, and the upper limit is more preferably 250 parts by weight.
The resin composition of the present invention preferably contains a thermoplastic resin. By using the thermoplastic resin, the resin composition of the present invention is excellent in flow characteristics, electrical characteristics, and bending resistance after curing.
Examples of the thermoplastic resin include: polyimide resins, phenoxy resins, polyamide resins, polyamideimide resins, polyvinyl acetal resins, and the like. Among them, polyimide resins and phenoxy resins are preferable from the viewpoint of effectively reducing the dielectric loss tangent and adjusting the melt viscosity regardless of the curing environment.
The thermoplastic resin may be used alone or in combination of 2 or more.
The thermoplastic resin has a preferable lower limit of 2000 and a preferable upper limit of 10 ten thousand in number average molecular weight. When the number average molecular weight of the thermoplastic resin is in this range, the resulting resin composition is further excellent in flow characteristics, electrical characteristics, and bending resistance after curing. The number average molecular weight of the thermoplastic resin is more preferably limited to 5000, and the upper limit is more preferably 5 ten thousand.
The content of the thermoplastic resin is preferably limited to 0.5 parts by weight, and the content is preferably limited to 50 parts by weight, based on 100 parts by weight of the curable resin. When the content of the thermoplastic resin is 0.5 parts by weight or more, the flow characteristics and flexibility resistance after curing of the obtained resin composition are further improved. When the content of the thermoplastic resin is 50 parts by weight or less, the heat resistance of the obtained cured product becomes more excellent. The more preferable lower limit of the content of the thermoplastic resin is 1 part by weight, and the more preferable upper limit is 30 parts by weight.
The resin composition of the present invention may contain a solvent. By using the solvent, the viscosity of the resin material can be controlled to a proper range, and the coatability of the resin material can be improved. The solvent may be used to obtain a slurry containing the inorganic filler. The above solvents may be used alone or in combination of 2 or more.
Examples of the solvent include: acetone, methanol, ethanol, butanol, 2-propanol, 2-methoxyethanol, 2-ethoxyethanol, 1-methoxy-2-propanol, 2-acetoxy-1-methoxypropane, toluene, xylene, methyl ethyl ketone, N-dimethylformamide, methyl isobutyl ketone, N-methyl-pyrrolidone, N-hexane, cyclohexane, cyclohexanone, naphtha as a mixture, and the like.
Among them, the boiling point of the solvent is preferably 200 ℃ or less, more preferably 180 ℃ or less, from the viewpoints of coatability and storage stability.
The term "boiling point" means a value measured under the condition of 101kPa or a value converted to 101kPa using a boiling point conversion chart or the like.
In 100 parts by weight of the resin composition of the present invention, the content of the solvent is preferably limited to 10 parts by weight, and the content of the solvent is preferably limited to 60 parts by weight. When the content of the solvent is within this range, the resin composition of the present invention is more excellent in coatability and the like. The lower limit of the content of the above solvent is more preferably 20 parts by weight, and the upper limit is more preferably 40 parts by weight.
The resin composition of the present invention may contain a reactive diluent within a range that does not hinder the object of the present invention.
The reactive diluent is preferably a reactive diluent having 2 or more reactive functional groups in 1 molecule from the viewpoint of adhesion reliability.
The resin composition of the present invention may further contain additives such as a coupling agent, a dispersant, a storage stabilizer, an anti-bleeding agent, a flux, a leveling agent, and the like.
Examples of the method for producing the resin composition of the present invention include: a method of mixing the curable resin, the curing agent, the inorganic filler, and optionally added solvent, etc. using a mixer.
Examples of the mixer include: a homogenizing and dispersing machine, a universal mixer, a Banbury mixer, a kneader, etc.
The resin composition of the present invention can be applied to a substrate film and dried to obtain a resin composition film containing the resin composition of the present invention, and the resin composition film is cured to obtain a cured product. The cured product of the resin composition of the present invention is also one of the present invention.
When a biphenyl type epoxy resin is contained as the above-mentioned curable resin, the cured product of the resin composition of the present invention has a preferable lower limit of 3 ppm/. Degree.C, and a preferable upper limit of 60 ppm/. Degree.C, in a temperature range of 25℃to 150 ℃. The heat resistance of the cured product of the resin composition of the present invention becomes more excellent. The lower limit of the above linear expansion coefficient is more preferably 5 ppm/DEG C, the upper limit is more preferably 40 ppm/DEG C, the upper limit is more preferably 28 ppm/DEG C, and the upper limit is particularly preferably 25 ppm/DEG C.
In the present specification, the "linear expansion coefficient" refers to a value measured by a Thermal Mechanical Analysis (TMA) method under conditions of a temperature rise rate of 5 ℃/min and a force of 33N. The cured product used for the measurement of the linear expansion coefficient can be obtained, for example, by heating the resin composition film having a thickness of about 40 μm at 190℃for 90 minutes.
When a biphenyl type epoxy resin is contained as the curable resin, the upper limit of the dielectric loss tangent at 23℃of the cured product of the resin composition of the present invention is preferably 0.015. The resin composition of the present invention can be suitably used for an interlayer insulating material such as a multilayer printed wiring board by setting the dielectric loss tangent of the cured product to 0.015 or less at 23 ℃. The upper limit of the dielectric loss tangent of the cured product at 23℃is more preferably 0.01, still more preferably 0.0035, and particularly preferably 0.003.
The "dielectric loss tangent" is a value measured at 5GHz using a dielectric constant measuring device and a network analyzer. The cured product of the "dielectric loss tangent" can be obtained by heating the resin composition film having a thickness of 40 μm to about 200 μm at 190℃for 90 minutes.
The resin composition of the present invention can be used for a wide variety of applications, and in particular, can be suitably used for applications of electronic materials requiring high heat resistance. For example, the present invention can be used for applications such as aviation and in-vehicle Electrical Control Units (ECU) and chip mounting agents for power devices using SiC and GaN. In addition, the present invention can be used for, for example, an adhesive for a power supply cover package (japanese: time) and an adhesive for a printed wiring board, an adhesive for a cover layer of a flexible printed circuit board, a copper-clad laminate, an adhesive for bonding a semiconductor, an interlayer insulating material, a prepreg, a sealant for an LED, an adhesive for a structural material, and the like.
Among them, the resin composition of the present invention is excellent in dielectric characteristics because the cured product has a low dielectric constant and a low dielectric loss tangent, and can be suitably used for a laminate film. The laminate film obtained by using the resin composition of the present invention is also one of the present invention.
Effects of the invention
According to the present invention, a polyfunctional active ester compound capable of providing a resin composition excellent in heat resistance and dielectric characteristics after curing can be provided. Further, according to the present invention, a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a laminate film using the resin composition can be provided.
Detailed Description
Hereinafter, the present invention will be described in further detail by way of examples, but the present invention is not limited to these examples.
Synthesis example 1 (preparation of multifunctional active ester Compound A)
130.96 parts by weight of 3-aminophenol was dissolved in 1400mL of N-methylpyrrolidone. To the obtained solution was added 208.20 parts by weight of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and the mixture was stirred at 25℃for 2 hours to react to obtain a solution of an amic acid compound. The obtained amic acid compound was added to 8400mL of 1mol/L acetic acid, and the precipitate was recovered. The obtained precipitate was heated at 300℃for 2 hours, whereby an imide compound having phenolic hydroxyl groups at both ends was obtained. 8.43 parts by weight of the obtained imide compound having phenolic hydroxyl groups at both ends and 3.64 parts by weight of triethylamine were dissolved in 60mL of tetrahydrofuran. To the resulting solution, 1.22 parts by weight of terephthaloyl chloride was added, and after stirring at 25℃for 4 hours, 2.63 parts by weight of 2-naphthoyl chloride was added, and further stirring at 25℃for 18 hours was carried out to carry out esterification reaction. As terephthaloyl chloride and 2-naphthoyl chloride, reagents manufactured by Tokyo chemical industry Co., ltd were used. After that, tetrahydrofuran was removed, and the remaining solid was washed with pure water, thereby obtaining a polyfunctional active ester compound a.
By the way, by 1 The polyfunctional active ester compound A was confirmed to contain the compound represented by the above formula (4) by H-NMR, GPC and FT-IR analysis. The number average molecular weight of the obtained polyfunctional active ester compound a was 1900.
The number average molecular weight was determined by GPC analysis (solvent: tetrahydrofuran, column: JAIGEL-2H-A, flow rate: 1.0 mL/min) and was obtained as a polystyrene-equivalent number average molecular weight.
Synthesis example 2 (preparation of multifunctional active ester Compound B)
The procedure of synthesis example 1 was repeated except that the content of terephthaloyl chloride was changed to 1.62 parts by weight, to obtain a polyfunctional active ester compound B.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound B contained a compound represented by the following formula (9). The number average molecular weight of the obtained polyfunctional active ester compound B was 2700.
[ chemical formula 9]
Synthesis example 3 (production of multifunctional active ester Compound C)
A polyfunctional active ester compound C was produced in the same manner as in synthesis example 1 except that 1.22 parts by weight of terephthaloyl chloride was changed to 1.22 parts by weight of isophthaloyl chloride.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound C contained a compound represented by the following formula (10). The number average molecular weight of the obtained polyfunctional active ester compound C was 1900.
[ chemical formula 10]
Synthesis example 4 (preparation of multifunctional active ester Compound D)
The procedure of synthesis example 3 was repeated except that the amount of isophthaloyl dichloride was changed to 1.62 parts by weight, to obtain a polyfunctional active ester compound D.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound D contained the compound represented by the following formula (11). The number average molecular weight of the obtained polyfunctional active ester compound D was 2700.
[ chemical formula 11]
Synthesis example 5 (production of multifunctional active ester Compound E)
A polyfunctional active ester compound E was obtained in the same manner as in synthesis example 1 except that 208.20 parts by weight of 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride was changed to 124.09 parts by weight of 4,4' -oxydiphthalic anhydride and the amount of the imide compound having phenolic hydroxyl groups at both terminals was changed from 8.43 parts by weight to 5.91 parts by weight.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound E contained the compound represented by the following formula (12). In addition, the number average molecular weight of the obtained polyfunctional active ester compound E was 1500.
[ chemical formula 12]
Synthesis example 6 (preparation of multifunctional active ester Compound F)
The procedure of synthesis example 5 was repeated except that the content of terephthaloyl chloride was changed to 1.62 parts by weight, to obtain a polyfunctional active ester compound F.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound F contained the compound represented by the following formula (13). The number average molecular weight of the obtained polyfunctional active ester compound F was 2100.
[ chemical formula 13]
Synthesis example 7 (preparation of multifunctional active ester Compound G)
The procedure of synthesis example 1 was repeated except for the following modifications, to obtain a polyfunctional active ester compound G.
That is, 208.20 parts by weight of 4,4' - (4, 4' -isopropylidenediphenoxy) diphthalic anhydride was changed to 124.09 parts by weight of 4,4' -oxydiphthalic anhydride, the amount of imide compound having phenolic hydroxyl groups at both ends was 5.91 parts by weight, and 1.22 parts by weight of terephthaloyl chloride was changed to 1.22 parts by weight of isophthaloyl chloride.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound G contained the compound represented by the following formula (14). The number average molecular weight of the obtained polyfunctional active ester compound G was 1500.
[ chemical formula 14]
Synthesis example 8 (preparation of multifunctional active ester Compound H)
The procedure of synthesis example 7 was repeated except that the amount of isophthaloyl dichloride was changed to 1.62 parts by weight, to obtain a polyfunctional active ester compound H.
By the way, by 1 The polyfunctional active ester compound H was confirmed to contain a compound represented by the following formula (15) by H-NMR, GPC and FT-IR analysis. In addition, the number average molecular weight of the obtained polyfunctional active ester compound H was 2100.
[ chemical formula 15]
Synthesis example 9 (preparation of multifunctional active ester Compound I)
A polyfunctional active ester compound I was produced in the same manner as in Synthesis example 1 except that 2.63 parts by weight of 2-naphthoyl chloride was changed to 1.94 parts by weight of benzoyl chloride.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound I contained the compound represented by the following formula (16). In addition, the number average molecular weight of the obtained polyfunctional active ester compound I was 1800.
[ chemical formula 16]
Synthesis example 10 (preparation of multifunctional active ester Compound J)
The procedure of synthesis example 9 was repeated except that the content of terephthaloyl chloride was changed to 1.62 parts by weight, to obtain a polyfunctional active ester compound J.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound J contained the compound represented by the following formula (17). The number average molecular weight of the obtained polyfunctional active ester compound J was 2600.
[ chemical formula 17]
Synthesis example 11 (preparation of multifunctional active ester Compound K)
A polyfunctional active ester compound K was produced in the same manner as in synthesis example 1, except that 1.22 parts by weight of terephthaloyl chloride was changed to 1.22 parts by weight of isophthaloyl chloride and 2.63 parts by weight of 2-naphthoyl chloride was changed to 1.94 parts by weight of benzoyl chloride.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound K contained the compound represented by the following formula (18). The number average molecular weight of the obtained polyfunctional active ester compound K was 1800.
[ chemical formula 18]
Synthesis example 12 (production of multifunctional active ester Compound L)
A polyfunctional active ester compound L was obtained in the same manner as in Synthesis example 11 except that the amount of isophthaloyl dichloride was changed to 1.62 parts by weight.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound L contained the compound represented by the following formula (19). The number average molecular weight of the obtained polyfunctional active ester compound L was 2600.
[ chemical formula 19]
Synthesis example 13 (preparation of multifunctional active ester Compound M)
130.96 parts by weight of 3-aminophenol was dissolved in 1400mL of N-methylpyrrolidone. To the obtained solution was added 208.20 parts by weight of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and the mixture was stirred at 25℃for 2 hours to react to obtain a solution of an amic acid compound. The obtained amic acid compound was added to 8400mL of 1mol/L acetic acid, and the precipitate was recovered. The obtained precipitate was heated at 300℃for 2 hours, whereby an imide compound having phenolic hydroxyl groups at both ends was obtained.
The obtained imide compound 8.43 parts by weight and triethylamine 4.86 parts by weight were dissolved in 130mL of tetrahydrofuran. To the resulting solution, 4.80 parts by weight of 2-naphthoyl chloride was added, and the mixture was stirred at 25℃for 4 hours to effect esterification. After that, tetrahydrofuran was removed under reduced pressure to obtain a polyfunctional active ester compound M.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound M contained the compound represented by the above formula (20).
[ chemical formula 20]
Synthesis example 14 (preparation of multifunctional active ester Compound N)
Using a vessel equipped with a stirrer, reflux condenser, dean-Stark (Dean-Stark) water separator, 21.8 parts by weight of 3-aminophenol was dissolved in 100mL of N-methylpyrrolidone. To the resulting solution was added 52.0 parts by weight of 4,4'- (4, 4' -isopropylidenediphenoxy) diphthalic anhydride, and the mixture was stirred at 25℃for 4 hours to effect a reaction. After 100mL of toluene was added to the resulting solution, reflux was performed at 150℃for 4 hours until no water was produced. After the completion of the reaction, toluene was removed from the obtained solution by using an evaporator, the obtained solution was added dropwise to 800mL of pure water, and the precipitate was filtered off.
The resulting precipitate (70.3 parts by weight) and triethylamine (20.2 parts by weight) were further dissolved in 200mL of N-methyl-2-pyrrolidone. To the resulting solution was added 28.1 parts by weight of benzoyl chloride, and the mixture was stirred at 25℃for 4 hours to effect a reaction. After the completion of the reaction, the resulting solution was added dropwise to 800mL of pure water, and the precipitate was filtered off, followed by vacuum drying to obtain a polyfunctional active ester compound N.
By the way, by 1 H-NMR, GPC and FT-IR analysis revealed that the polyfunctional active ester compound N was not represented by the above formula (1).
Examples 1 to 12 and comparative examples 1 to 3
Cyclohexanone as a solvent was added to each of the materials in the compounding ratios shown in tables 1 and 2, and the mixture was stirred at 1200rpm for 4 hours using a stirrer, to obtain a resin composition. The compositions of tables 1 and 2 show solid components excluding the solvent.
The obtained resin composition was applied on a release treated surface of a PET film having a thickness of 25. Mu.m, using an applicator. XG284 (manufactured by Toli Co., ltd.) was used as the PET film. Thereafter, the solvent was evaporated by drying in a Gill's oven at 100℃for 2.5 minutes. Thus, an uncured laminated film having a PET film and a resin composition layer on the PET film was obtained, the thickness of the resin composition layer was 40 μm, and the residual amount of the solvent was 1.0% by weight or more and 7.0% by weight or less.
< evaluation >
The uncured laminated films obtained in examples and comparative examples were evaluated as follows. The results are shown in tables 1 and 2.
(Heat resistance)
The uncured laminate films obtained in examples and comparative examples were heated at 190℃for 90 minutes, and then the base PET film was peeled off to obtain cured products. The linear expansion coefficient of the obtained cured product was measured at a temperature range of 25℃to 150℃under a force of 33N at a heating rate of 5℃per minute using a thermal mechanical analyzer. As a thermal mechanical analysis device, TMA7100 (manufactured by Hitachi High-Tech Science Co., ltd.) was used.
The heat resistance was evaluated by setting "O" when the linear expansion coefficient was 25 ppm/DEG C or less, setting "delta" when the linear expansion coefficient was more than 25 ppm/DEG C and 28 ppm/DEG C or less, and setting "X" when the linear expansion coefficient was more than 28 ppm/DEG C.
(dielectric Properties)
The uncured laminate films obtained in examples and comparative examples were heated at 190℃for 90 minutes, and then the base PET film was peeled off to obtain cured products. The obtained cured product was cut into a size of 2mm in width and 100mm in length. The dielectric loss tangent of the cured product after cutting was measured by a cavity resonance method at 23℃and a frequency of 5GHz using a cavity resonance perturbation method dielectric constant measuring device and a network analyzer. CP521 (manufactured by kanto electronics application development) was used as a dielectric constant measuring device by the cavity perturbation method, and N5224A PNA (manufactured by Keysight Technologies) was used as a network analyzer.
The dielectric characteristics were evaluated by setting the dielectric loss tangent to 0.0025 or less as "verygood", setting the dielectric loss tangent to 0.003 or less to "good", setting the dielectric loss tangent to 0.003 or less to "delta", setting the dielectric loss tangent to 0.0035 or less to "×", and setting the dielectric loss tangent to 0.0035 or more to "×".
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Industrial applicability
According to the present invention, a polyfunctional active ester compound capable of providing a resin composition excellent in heat resistance and dielectric characteristics after curing can be provided. Further, according to the present invention, a resin composition using the polyfunctional active ester compound, a cured product of the resin composition, and a laminate film using the resin composition can be provided.
Claims (9)
1. A polyfunctional active ester compound characterized by being represented by the following formula (1),
in the formula (1), R 1 R is R 2 Are each the same or different, andand is an optionally substituted aryl group, X is each independently an oxygen atom, a sulfonyl group, a carbonyl group or a group represented by the following formula (3), wherein in formula (3), X is a bonding position, Y is an optionally substituted arylene group, n is an integer of 1 to 5,
2. the polyfunctional active ester compound according to claim 1, having a number average molecular weight of 1300 or more and 5500 or less.
3. The polyfunctional active ester compound according to claim 1 or 2, wherein Y in formula (1) is 1, 3-phenylene or 1, 4-phenylene.
4. The polyfunctional active ester compound of claim 1 or 2 wherein R in said formula (1) 1 R is R 2 Is a group represented by the following formula (2),
in the formula (2), R 3 Each independently is a hydrogen atom or an aliphatic group, and each is a bonding position.
5. The polyfunctional active ester compound according to claim 1 or 2, wherein X in the formula (1) is an oxygen atom or a group represented by the formula (3).
6. A resin composition comprising a curable resin and the polyfunctional active ester compound of claim 1, 2, 3,4 or 5.
7. The resin composition according to claim 6, further comprising an inorganic filler.
8. A cured product of the resin composition according to claim 6 or 7.
9. A laminated film comprising the resin composition according to claim 6 or 7.
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| PCT/JP2020/018260 WO2020226118A1 (en) | 2019-05-07 | 2020-04-30 | Multifunctional active ester compound, resin composition, cured product and buildup film |
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| US4657977A (en) * | 1985-10-04 | 1987-04-14 | General Electric Company | Poly(etherimide-carbonate) block copolymers and polymer blends containing same |
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| JP6939017B2 (en) | 2016-03-30 | 2021-09-22 | 荒川化学工業株式会社 | Polyimide, polyimide adhesive, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate and printed wiring board, and multilayer wiring board and its manufacturing method |
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2020
- 2020-04-30 CN CN202080033314.5A patent/CN113785008B/en active Active
- 2020-04-30 JP JP2020530410A patent/JP7480040B2/en active Active
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- 2020-04-30 WO PCT/JP2020/018260 patent/WO2020226118A1/en active Application Filing
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| JP2004035858A (en) * | 2002-07-08 | 2004-02-05 | Kanegafuchi Chem Ind Co Ltd | Heat-curable resin composition, heat-curable resin solution, and heat-curable resin sheet |
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| JP7480040B2 (en) | 2024-05-09 |
| CN113785008A (en) | 2021-12-10 |
| WO2020226118A1 (en) | 2020-11-12 |
| KR20220006038A (en) | 2022-01-14 |
| TW202106748A (en) | 2021-02-16 |
| TWI830911B (en) | 2024-02-01 |
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